The Dr. Oz Show host talked to ET exclusively about the late Mob Wives star's demeanor during her recent appearance on the program, which aired on Tuesday.

"By the time she came on the show, she really had wanted to get things off her chest, to say things she knew she needed to say before the end, because she had weeks to months, not months to years left," he said. "The most important emotion I heard from Big Ang outside the show was fear -- she was scared. I think she knew the end was grasping at her, that she was looking over the abyss of death, a darkness down there that we all fear, and she knew that it was close."

"You couldn't take Big Ang's bigness from her -- she earned that name with 55 years of hard living and doing what she thought needed to be done," Dr. Oz smiled. "But, she was somber. I think when you look back on your life and you realize there's things you could have done differently -- you also appreciate that because of the cards you were dealt, you may not have all the options, you might not have the opportunity to see your grandkids grow up, you may not have the opportunity to see all your children be the people they can become -- it's painful. I think there was a bit of remorse that I sensed from her throughout these conversations."

Dr. Oz said one big reason she came on the show was to warn people about smoking cigarettes.

"I think the big legacy she's leaving us, the big reason she came on the show, was to make sure everyone knew that cigarettes had taken her life," he stressed. "She started young, like so many, but like so many, by the time she realized she didn't want to smoke anymore, it was too late to stop -- at least she felt that way. And she joked on the show about how she got the diagnosis of throat cancer, and as she walked out of the hospital, she took the pack of cigarettes and tossed them in the trash. And she quit cold turkey, but it was a little late."

As for the late reality star's bombshell on his show that she left her husband, Neil Murphy, amid her cancer battle, Dr. Oz said he wasn't surprised that Murphy was by her side during her final hours.

"I think Big Ang loved her husband dearly," he mused. "Her decision to separate was based more on the fact that she had to focus on Big Ang, especially at this dire time. She couldn't afford to focus on other people. And I think she realized that she had been providing a lot for many years, but that doesn't change the way how you feel about people -- you still love them dearly."

"I am saddened to say that at 3:01 a.m. Ang lost her battle with cancer," Graziano said. "She passed peacefully surrounded by friends and family. My heart is broken for her whole family -- especially her children and grandchildren and I will never forget her. Her presence brought sheer happiness to anyone that was around her and I am honored to have called her a friend. Please respect her family's privacy at this time as they mourn the loss of such an amazing woman."